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DOE OSTI2024

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe2O3, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1993

Optical characterization of LDEF contaminant film

Dark brown molecular film deposits were found at numerous locations on the Long Duration Exposure Facility (LDEF) and have been documented in great detail by several investigators. The exact deposition mechanism for these deposits is as yet unknown, although direct and scattered atomic oxygen, and solar radiation interacting with materials outgassing products have all been implicated in the formation process. Specimens of the brown molecular film were taken from below the flange of the experimental tray located at position D10 on the LDEF. The tray was one of two, comprising the same experiment, the other being located on the wake facing side of the LDEF satellite at position B4. Having access to both trays, we were able to directly compare the effect that orientation with respect to the atomic oxygen flux vector had on the formation of the brown molecular film deposits. The film is thickest on surfaces facing toward the exterior, i.e. the tray corner, as can be seen by comparing the lee and wake aspects of the rivets. The patterns appear to be aligned not with the velocity vector but with the corner of the tray suggesting that flux to the surface is due to scattered atomic oxygen rather than direct ram impingement. The role of scattered flux is further supported by more faint plume patterns on the sides of the tray. The angle of these plumes is strongly aligned with the ram direction but the outline of the deposit implies that incident atoms are scattered by collisions with the edges of the opening resulting in a directed, but diffuse, flux of atomic oxygen to the surface. Spectral reflectance measurements in the 2 to 10 micron (4000 to 1000 wavenumbers) spectral range are presented for the film in the 'as deposited' condition and for the free standing film. The material was analyzed by FTIR (Fourier Transform Infrared) microspectroscopy using gold as the reference standard. The 'as deposited' specimen was on an aluminum rivet taken from beneath the tray flange while the free film was obtained by chipping some of the material from the rivet. The transmission spectrum over the 2 to 10 micron range for the free film is presented. This spectrum appears to be essentially the same as that presented by Crutcher et.al. for films formed at vent sites which faced into the ram direction and suggested to originate from urethanes and silicones used on the LDEF. Banks et. al. state that silicones, when exposed to atomic oxygen, release polymeric scission fragments which deposit on surfaces and form a glassy, dark contaminant layer upon further atomic oxygen exposure and solar irradiation.

Blakkolb, Brian K.↗

NASA NTRS1989

Heterodyne spectroscopy of the J = 17-16 CO line in Orion

We have obtained high-resolution spectra of the 153 micrometers J = 17-16 CO line in the BN-KL region of Orion using a laser heterodyne spectrometer. The line shows broad wings (30 km s-1 FWHM at BN) characteristic of the plateau emission as well as a narrower component probably associated with the quiescent gas in the molecular ridge. From an analysis of the plateau emission together with that observed in lower J CO transitions, we derive an excitation temperature of 180 +/- 50 K and minimum column density of 1 x 10(18) cm-2 for CO in this component, which constitutes 80% of the total integrated intensity of the J = 17-16 line near BN. The peak intensity of the narrower component observed at 0.8 km s-1 resolution increases relative to that of the plateau component toward theta 1C and away from BN, while the width decreases from 10 to 4 km s-1 (FWHM).

NASA Discipline Number 52-60↗

DOE OSTI2021

Transport of Protostellar Cosmic Rays in Turbulent Dense Cores

We report recent studies have suggested that low-energy cosmic rays (CRs) may be accelerated inside molecular clouds by the shocks associated with star formation. We use a Monte Carlo transport code to model the propagation of CRs accelerated by protostellar accretion shocks through protostellar cores. We calculate the CR attenuation and energy losses and compute the resulting flux and ionization rate as a function of both radial distance from the protostar and angular position. We show that protostellar cores have nonuniform CR fluxes that produce a broad range of CR ionization rates, with the maximum value being up to two orders of magnitude higher than the radial average at a given distance. In particular, the CR flux is focused in the direction of the outflow cavity, creating a "flashlight" effect and allowing CRs to leak out of the core. The radially averaged ionization rates are less than the measured value for the Milky Way of ζ ≈ 10 -16 s -1 ; however, within r ≈ 0.03 pc from the protostar, the maximum ionization rates exceed this value. We show that variation in the protostellar parameters, particularly in the accretion rate, may produce ionization rates that are a couple of orders of magnitude higher or lower than our fiducial values. Finally, we use a statistical method to model unresolved subgrid magnetic turbulence in the core. We show that turbulence modifies the CR spectrum and increases the uniformity of the CR distribution but does not significantly affect the resulting ionization rates.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Non-adiabatic quantum interference and complex formation in ultracold collisions of Rb with KRb

Ultracold elastic collisions of 87 Rb with 40 K 87 Rb in its ground vibrational and rotational state are investigated using a first principles based theoretical methodology. Full-dimensional ab initio computed potential energy surfaces are reported that include the two lowest-lying electronic states, their conical intersection, non-adiabatic couplings and an accurate long-range behavior. A numerically exact time-independent quantum dynamics method in hyperspherical coordinates is used to compute the elastic scattering cross sections, rate coefficients and collision lifetime spectrum. The quantum scattering calculations include all degrees of freedom and treat both electronic states and their non-adiabatic couplings using a two-state diabatic representation. The theoretically computed elastic rate coefficient is in good agreement with the recently reported experimental value. Significant non-adiabatic quantum interference effects are shown to originate from the unique properties of ultracold collisions and the geometric phase associated with the conical intersection. A high-resolution collision energy grid is used to investigate the origin of the experimentally reported long-lived 3-body collision complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1997

Nitrogen sulfide in giant molecular clouds

We report a survey for nitrogen sulfide (NS) toward regions of massive star formation. NS was observed by means of its 2 pi 1/2, J = 3/2 --> 1/2, J = 5/2 --> 3/2, and J = 7/2 --> 5/2 transitions at 69, 115, and 161 GHz, respectively, and was detected toward 12 of 14 giant molecular clouds (GMCs) observed. Analysis of the hyperfine component relative line strengths suggests that NS emission is optically thin toward these sources, with the possible exception of Sgr B2(M). The fractional abundance of NS relative to molecular hydrogen is best defined for the Orion molecular cloud, where it is typically (1-4) x 10(-10), which is about an order of magnitude larger than found by some recent gas-phase chemistry models developed for quiescent clouds. Toward OMC-1, the NS integrated intensity is strongly peaked toward KL, but also extends all along the Orion ridge, resembling the distribution of SO and CH3OH. We have identified a spectral feature seen toward several sources as the ortho-NKK = 4(04) --> 3(13) J = 3 --> 2, fine-structure component of methylene (CH2; cf. Hollis, Jewell, & Lovas). We also report the first detection of the SO+ 2 pi 1/2, J = 3/2 --> 1/2, parity-e transition toward W51(MS) and L134N.

NASA Discipline Exobiology↗

DOE OSTI2022

Characterization of single-shot attosecond pulses with angular streaking photoelectron spectra

Most of the traditional attosecond pulse retrieval algorithms are based on a so-called attosecond streak camera technique, in which the momentum of the electron is shifted by an amount depending on the relative time delay between the attosecond pulse and the streaking infrared pulse. Thus, temporal information of the attosecond pulse is encoded in the amount of momentum shift in the streaked photoelectron momentum spectrogram S(p,τ), where p is the momentum of the electron along the polarization direction and τ is the time delay. An iterative algorithm is then employed to reconstruct the attosecond pulse from the streaking spectrogram. This method, however, cannot be applied to attosecond pulses generated from free-electron x-ray lasers where each single shot is different and stochastic in time. However, using a circularly polarized infrared laser as the streaking field, a two (or three)-dimensional angular streaking electron spectrum can be used to retrieve attosecond pulses for each shot, as well as the time delay with respect to the circularly polarized IR field. Here we show that a retrieval algorithm previously developed for the traditional streaking spectrogram can be modified to efficiently characterize single-shot attosecond pulses. The methods have been applied to retrieve 188 single shots from recent experiments. We analyze the statistical behavior of these 188 pulses in terms of pulse duration, bandwidth, pulse peak energy, and time delay with respect to the IR field. Furthermore, the retrieval algorithm is efficient and can be easily used to characterize a large number of shots in future experiments for attosecond pulses at free-electron x-ray laser facilities.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1996

Spectroscopic evidence for interstellar ices in comet Hyakutake

Volatile compounds in comets are the most pristine materials surviving from the time of formation of the Solar System, and thus potentially provide information about conditions that prevailed in the primitive solar nebula. Moreover, comets may have supplied a substantial fraction of the volatiles on the terrestrial planets, perhaps including organic compounds that played a role in the origin of life on Earth. Here we report the detection of hydrogen isocyanide (HNC) in comet Hyakutake. The abundance of HNC relative to hydrogen cyanide (HCN) is very similar to that observed in quiescent interstellar molecular clouds, and quite different from the equilibrium ratio expected in the outermost solar nebula, where comets are thought to form. Such a departure from equilibrium has long been considered a hallmark of gas-phase chemical processing in the interstellar medium, suggesting that interstellar gases have been incorporated into the comet's nucleus, perhaps as ices frozen onto interstellar grains. If this interpretation is correct, our results should provide constraints on the temperature of the solar nebula, and the subsequent chemical processes that occurred in the region where comets formed.

Non-NASA Center↗

NASA NTRS2021

A Ring Accelerator? Unusual Jet Dynamics in the IceCube Candidate PKS 1502+106

On 2019/07/30.86853 UT, IceCube detected a high-energy astrophysical neutrino can-didate. The Flat Spectrum Radio Quasar PKS 1502+106 is located within the 50 percent uncertainty region of the event. Our analysis of 15 GHz Very Long Baseline Ar-ray (VLBA) and astrometric 8 GHz VLBA data, in a time span prior and after theIceCube event, reveals evidence for a radio ring structure which develops with time.Several arc-structures evolve perpendicular to the jet ridge line. We find evidence forprecession of a curved jet based on kinematic modelling and a periodicity analysis.An outflowing broad line region (BLR) based on the C IV line emission (Sloan Dig-ital Sky Survey, SDSS) is found. We attribute the atypical ring to an interaction ofthe precessing jet with the outflowing material.We discuss our findings in thecontext of a spine-sheath scenario where the ring reveals the sheath andits interaction with the surroundings (NLR clouds).We find that the radioemission is correlated with theγ-ray emission, with radio lagging theγ-rays. Basedon theγ-ray variability timescale, we constrain theγ-ray emission zone to the BLR(30-200rg) and within the jet launching region. We discuss that the outflowing BLRprovides the external radiation field forγ-ray production via external Compton scat-tering.The neutrino is most likely produced by proton-proton interactionin the blazar zone (beyond the BLR), enabled by episodic encounters ofthe jet with dense clouds, i.e. some molecular cloud in the NLR.

S Britzen↗

DOE OSTI2021

Bound state dynamics in the long-range spin- 1 2 XXZ model

Experimental platforms based on trapped ions, cold molecules, and Rydberg atoms have made possible the investigation of highly nonlocal spin-1 / 2 Hamiltonians with long-range couplings. Here, we study the effects of such nonlocal couplings in the long-range spin-1 / 2 XXZ Heisenberg Hamiltonian. Here, we calculate explicitly the two-spin energy spectrum, which describes all possible energetic configurations of two spins pointing in a specific direction embedded in a background of spins with opposite orientation. For fast decay of the spin-spin couplings, we find that the two-spin energy spectrum is characterized by well-defined discrete values, corresponding to bound states, separated by a set of continuum states describing the scattering region. In the deep long-range regime instead, the bound states disappear as they get incorporated by the scattering region. The presence of two-spin bound states results to be crucial to determine both two- and many-spin dynamics. On one hand, radically different two-spin spreadings can be observed by tuning the decay of the spin couplings. On the other hand, two-spin bound states enable the dynamical stabilization of effective antiferromagnetic states in the presence of ferromagnetic couplings. Finally, we propose a novel scheme based on a trapped-ion quantum simulator to experimentally realize the long-range XXZ model and to study its out-of-equilibrium properties.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1993

Spontaneous assembly of a self-complementary oligopeptide to form a stable macroscopic membrane

A 16-residue peptide [(Ala-Glu-Ala-Glu-Ala-Lys-Ala-Lys)2] has a characteristic beta-sheet circular dichroism spectrum in water. Upon the addition of salt, the peptide spontaneously assembles to form a macroscopic membrane. The membrane does not dissolve in heat or in acidic or alkaline solutions, nor does it dissolve upon addition of guanidine hydrochloride, SDS/urea, or a variety of proteolytic enzymes. Scanning EM reveals a network of interwoven filaments approximately 10-20 nm in diameter. An important component of the stability is probably due to formation of complementary ionic bonds between glutamic and lysine side chains. This phenomenon may be a model for studying the insoluble peptides found in certain neurological disorders. It may also have implications for biomaterials and origin-of-life research.

Non-NASA Center↗

DOE OSTI2022

Controlling Structural, Electronic, and Energy Flow Dynamics of Catalytic Processes through Tailored Nanostructures

MoS 2 (molybdenum disulfide) is a highly-versatile catalyst material for support of numerous reactions from hydrodesulfurization and denitrogenation to the focus of this renewal proposal: hydrogenation of CO/CO 2 towards (higher) alcohols. At the same time, MoS 2 is a non-toxic, environmentally-benign and rather inert material- which under ambient conditions for some time has served as a lubricant and, more recently, as next-generation electronic material. The apparent contrast between inertness and stability in ambient, and catalytic activity under reactive conditions is puzzling and calls for a synergistic theoretical and experimental investigation with the long-term objective of enabling the rational design of MoS 2 -based catalysts for alcohol-formation reactions by providing a microscopic understanding of the environmental factors that determines site activity and selectivity. Our research project seeks answers to the questions (a) what conformation does MoS 2 adopt under reaction conditions (as opposed to that under ultrahigh vacuum and low temperatures)?; (b) what reaction pathways exist on such a material?; (c) how can the local environment of the active sites be manipulated so as to make MoS 2 an efficient catalyst for production of higher alcohol from syngas? In particular, research strategies will explore how the basal plane composed of sulfur atoms can be activated so as to exhibit a reactivity of its own, by addressing three research targets and building on extensive preliminary and enabling work: (1) vacancies and vacancy aggregates on the basal plane; (2) non-local catalyst transformation through alkali doping, hydrogenation and phase transition; (3) fabrication of a metal-nanoparticle-activated MoS 2 system, in which particle anchoring, reactive sites and pathways as well as selectivity are controlled by design, as an example of predictive development of a catalyst material,. All strategies are directed to improve the efficacy of the key reactive sites and selectivity of chemical pathways by design, to replace the inefficient methodology of trial and error in catalyst development. This research project represents a synergistic combination of computational guidance, foundational surface-science-based experiments and validation under reactive conditions that aims at transformative new insights into the working of MoS 2 -based hydrogenation-catalysts, a topic squarely at the center of the interest of DOE BES. Guided and led by Talat Rahman, a computational physicist, this project will apply density functional theory to understand structure, reaction pathways and chemical potentials associated with MoS 2 -based CO/CO 2 hydrogenation, augmented by kinetic Monte Carlo methods for reaction rates and prefactors as well as ab-initio molecular dynamics for evaluation of thermal stability. Complementary experimental input and validation will originate from co-PI Ludwig Bartels, a physical chemist and materials scientist, whose group focuses on local imaging and preparation of MoS 2 materials, from co-PI Peter Dowben, an experimental physicist, whose group is expert in the spectroscopy of occupied and unoccupied electronic states, and from senior collaborator Michael White of Brookhaven National Laboratory, whose group generates high-resolution electronic and activity information on size-selected well-defined metal chalcogenide clusters. This collaborative effort will enable a comprehensive understanding of the correlation of structural integrity and catalytic activity of MoS 2 in forms ranging from extended films to individual particles with known geometries and binding sites. Alcohol formation from syngas is a rapidly emerging application that has great potential through facile, economic, and decentralized biomass gasification. CO 2 activation is one of the most pressing concerns of our time: increasing CO 2 levels in the atmosphere change the climate and expose the globe to environmental transformations with the potential for enormous economic and societal impact. We will investigate CO/CO 2 hydrogenation via an interdisciplinary research collaboration with established synergy – one that, in accordance with the mission of the DOE, involves accredited Hispanic-Serving Institutions and that, through student exchange with international collaborators and National Labs, will directly benefit a broad spectrum of communities and generate human resources in sciences essential to their future.

2D materials↗

NASA NTRS2000

Regolith Evolved Gas Analyzer

The Regolith Evolved Gas Analyzer (REGA) is a high-temperature furnace and mass spectrometer instrument for determining the mineralogical composition and reactivity of soil samples. REGA provides key mineralogical and reactivity data that is needed to understand the soil chemistry of an asteroid, which then aids in determining in-situ which materials should be selected for return to earth. REGA is capable of conducting a number of direct soil measurements that are unique to this instrument. These experimental measurements include: (1) Mass spectrum analysis of evolved gases from soil samples as they are heated from ambient temperature to 900 C; and (2) Identification of liberated chemicals, e.g., water, oxygen, sulfur, chlorine, and fluorine. REGA would be placed on the surface of a near earth asteroid. It is an autonomous instrument that is controlled from earth but does the analysis of regolith materials automatically. The REGA instrument consists of four primary components: (1) a flight-proven mass spectrometer, (2) a high-temperature furnace, (3) a soil handling system, and (4) a microcontroller. An external arm containing a scoop or drill gathers regolith samples. A sample is placed in the inlet orifice where the finest-grained particles are sifted into a metering volume and subsequently moved into a crucible. A movable arm then places the crucible in the furnace. The furnace is closed, thereby sealing the inner volume to collect the evolved gases for analysis. Owing to the very low g forces on an asteroid compared to Mars or the moon, the sample must be moved from inlet to crucible by mechanical means rather than by gravity. As the soil sample is heated through a programmed pattern, the gases evolved at each temperature are passed through a transfer tube to the mass spectrometer for analysis and identification. Return data from the instrument will lead to new insights and discoveries including: (1) Identification of the molecular masses of all of the gases liberated from heated soil samples; (2) Identification of the asteroid soil mineralogy to aid in the selection process for returned samples; (3) Existence of oxygen in the asteroid soil and the potential for in-situ resource utilization (ISRU); and (4) Existence of water and other volatiles in the asteroid soil. Additional information is contained in the original extended abstract.

Hoffman, John H.↗

NASA NTRS1995

The formation of protostellar disks. 2: Disks around intermediate-mass stars

Hydrodynamical calculations of the evolution of a collapsing, rotating axisymmetric 10 solar masses molecular clump, including the effects of radiative acceleration but without magnetic fields, are represented. The initial cloud is assumed to be uniformly rotating, centrally condensed sphere with rho is proportional to r(exp -2). Several cases are considered, in which both the overall clump size and the total amount of angular momentum are varied. The calculations show how a warm, quasi-hydrostatic disk surrounding a central unresolved core of only a few solar masses forms and grows in size and mass. The disk is encased in two distinct accretion shock fronts, both of which are several scale heights above the equatorial plane. At the end of the calculation of our standard case, the central unresolved region is found to have a mass of 2.7 solar masses and a ratio of rotational to gravitational energy of approximately 0.45, sufficiently large to be unstable to nonaxisymmetric perturbations. In addition, the inner portions of the disk containing most of the mass are unstable according to the local Toomre criterion, implying that also in this region nonaxisymmetric perturbations will lead to rapid evolution. Under the assumption that gravitational torques would transport angular momentum out of this region, a central core of less than or approximately 8 solar masses with a stable disk of greater than or approximately = 2 solar masses should result. Frequency-dependent radiative transfer calculations of the standard case at selected ages show how the continuum spectrum of the structure depends on the disk's orientation and age and how the observed isophotal contours vary with wavelength. Because of the strong dependence on viewing angle, continuum spectra alone should not be used to estimate the evolutionary stage of development of these objects. Comparable results were obtained for the other cases considered.

Yorke, Harold W.↗

NASA NTRS1998

Molecular Processes in Comets

The research focused on molecular hydrogen and its response to ultraviolet radiation, photoelectron impact excitation and X-ray radiation and on the interpretation of the ultraviolet spectra of the Jupiter dayglow and auroras. A systematic effort was made to obtain reliable rate coefficients for rovibrational energy transfer of H2, particularly in collisions with hydrogen atoms. We carried out elaborate quantum-mechanical calculations of the scattering of H and H2 on what had been characterized as a reliable potential energy surface of the H3 molecular system. These calculations took into account reactive channels and rate coefficients for ortho-para transitions were obtained. Quantal calculations are too complex to be applied to all the possible rovibrational transitions and we turned to a semi-classical method. With it we calculated rate coefficients for transitions, reactive and non-reactive, for all the rovibrational levels. We carried out the calculations for three of the available H3 potential energy surfaces. We discovered an unexpected sensitivity of the rate coefficients for the non-reactive channels to the potential energy surface. This discovery stimulated more thorough investigations of the potential energy surface elsewhere and to the construction of a new surface. We have used it in further semi-classical calculations in work that will shortly be 2 completed and which, together with new quantum-mechanical calculations should comprise a set of reliable rate coefficients that can be used in discussions of H2 on the Jovian planets. We carried out a detailed study of the Jovian ultraviolet dayglow. There has been a long-running argument about the dayglow on Jupiter. There are two sources of excitation: fluorescence and photoelectron impact excitation. It had been argued that a third source "the electron glow" was needed to bring theory and observation into agreement. We believe we have shown conclusively that the third source is unnecessary. We have achieved a close quantitative agreement between the predicted spectrum arising from fluorescence and photoelectrons and the measured spectrum. We also demonstrated a method by which the presence of HD could be established observationary. Similar calculations were carried out of the ultraviolet spectra of the Jovian auroras. We again found close agreement. Indeed, the agreement was so detailed we were able to derive the temperature of the atmosphere. We found, contrary to the standard model of the time, a high temperature between 400 K and 600 K and established the presence of a significant temperature gradient. A large temperature gradient was indeed found by direct sampling with the Jupiter probe.

Dalgarno, A.↗

DOE OSTI2024

Vibrational Cooper minima used to verify the dissociation pathway induced by a short intense laser pulse

Vibrational Cooper minima due to weak dipole coupling were previously observed in strong-field dissociation of H 2⁡ + as minima in the kinetic-energy-release (KER) spectrum [McKenna et al., Phys. Rev. Lett. 103, 103006 (2009)]. We demonstrate in two independent experiments that these vibrational Cooper minima occur more generally and can be used as “fingerprints” to identify the final electronic state in the dissociation pathway. In the first experiment, we show the wavelength dependence of the vibrational Cooper minima observed in the KER spectrum of O 2⁢ + dissociation induced by 396- and 264-nm photons. These minima appear at the locations predicted by our first-order perturbation-theory calculations. In the second experiment, a delay-dependent KER spectrum is obtained from O 2 using an ionizing pump and a dissociating probe, then Fourier-transformed to generate a spin-rotation quantum beat spectrum of O 2 ⁢+ . As a result, this spectrum shows vibrational Cooper minima at the expected locations, confirming their presence in another observable. In this case, these minima are used to identify the dissociation pathway.

Molecular dissociation↗

NASA NTRS1997

Identification of defective illegitimate recombinational repair of oxidatively-induced DNA double-strand breaks in ataxia-telangiectasia cells

Ataxia-telangiectasia (A-T) is an autosomal-recessive lethal human disease. Homozygotes suffer from a number of neurological disorders, as well as very high cancer incidence. Heterozygotes may also have a higher than normal risk of cancer, particularly for the breast. The gene responsible for the disease (ATM) has been cloned, but its role in mechanisms of the disease remain unknown. Cellular A-T phenotypes, such as radiosensitivity and genomic instability, suggest that a deficiency in the repair of DNA double-strand breaks (DSBs) may be the primary defect; however, overall levels of DSB rejoining appear normal. We used the shuttle vector, pZ189, containing an oxidatively-induced DSB, to compare the integrity of DSB rejoining in one normal and two A-T fibroblast cells lines. Mutation frequencies were two-fold higher in A-T cells, and the mutational spectrum was different. The majority of the mutations found in all three cell lines were deletions (44-63%). The DNA sequence analysis indicated that 17 of the 17 plasmids with deletion mutations in normal cells occurred between short direct-repeat sequences (removing one of the repeats plus the intervening sequences), implicating illegitimate recombination in DSB rejoining. The combined data from both A-T cell lines showed that 21 of 24 deletions did not involve direct-repeats sequences, implicating a defect in the illegitimate recombination pathway. These findings suggest that the A-T gene product may either directly participate in illegitimate recombination or modulate the pathway. Regardless, this defect is likely to be important to a mechanistic understanding of this lethal disease.

Non-NASA Center↗

DOE OSTI2023

Biomimetic Light Harvesting Complexes Based on Self-Assembled Dye-DNA Nanostructures (Final Technical Report)

A fundamental limitation in the development of artificial molecular light harvesting structures is that generally if one places pigment molecules close enough to achieve very high energy transfer efficiency and absorbance cross section, the dyes interact in such a way that self-quenching occurs. This limits both the optical cross section and the overall efficiency of light capture in such systems. Nature overcomes this problem and achieves efficient energy transfer without self-quenching by controlling the environment, vibration characteristics, orientation and dynamics of the pigments involved in light harvesting. Natural light harvesting systems have evolved highly intricate chromophore architectures of protein-bound organic molecules that absorb and funnel solar energy with high efficiency and fast transfer rates using elegant excitonic circuitries. Nature achieves this precise control over the properties of pigment complexes by using specific proteins as templates to guide the formation of very well-defined pigment aggregates, groups of pigment molecules that are in close enough contact to undergo excitonic interactions resulting in new electronic properties that were not present in the monomer. In synthetic systems, pigment aggregates are well known, and J-aggregates and H-aggregates have been long studied for their unique properties. In Nature, the chlorosomes of green bacteria form what appear to be classical J-aggregates and the light harvesting complexes of purple nonsulfur bacteria form ring structures that have many of the properties of J-aggregates such as a red-shifted absorbance spectrum and excited states that are delocalized over multiple pigment molecules. These photosynthetic systems leverage the spectral and enhanced transport properties of J-like aggregates to achieve fast exciton transport within the antenna and thus high light-harvesting efficiency. The close interaction of the pigments results in substantial electronic coupling that lifts the degeneracy of excitonic states and therefore modifies the absorption and emission spectra of the monomer. In the case of J-aggregation, lower energy excitonic states acquire significant oscillator strength, resulting in a characteristic bathochromic shift of the absorption and fluorescence and often superradiant delocalized exciton states.

77 NANOSCIENCE AND NANOTECHNOLOGY↗